EP1824338B1 - 3-cyclopropyl-4-(3-amino-2-methylbenzoyl)pyrazoles et leur utilisation comme herbicides - Google Patents

3-cyclopropyl-4-(3-amino-2-methylbenzoyl)pyrazoles et leur utilisation comme herbicides Download PDF

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Publication number
EP1824338B1
EP1824338B1 EP05807937A EP05807937A EP1824338B1 EP 1824338 B1 EP1824338 B1 EP 1824338B1 EP 05807937 A EP05807937 A EP 05807937A EP 05807937 A EP05807937 A EP 05807937A EP 1824338 B1 EP1824338 B1 EP 1824338B1
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EP
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Prior art keywords
alkyl
methyl
alkoxy
group
ethyl
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English (en)
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EP1824338A1 (fr
Inventor
Monika Schmitt
Lothar Willms
Ines Heinemann
Andreas Van Almsick
Thomas Auler
Martin Hills
Heinz Kehne
Dieter Feucht
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Bayer CropScience AG
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Bayer CropScience AG
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the invention relates to the technical field of herbicides, in particular that of herbicides for the selective control of weeds and grass weeds in crops.
  • the object of the present invention is therefore to provide herbicidally active compounds with improved herbicidal properties and improved compatibility with crop plants, in particular with respect to corn, rice, cereals and soybean, in comparison to the compounds known from the prior art.
  • R 5 is hydrogen
  • the compounds of the formula (I) according to the invention can occur in different tautomeric structures, depending on external conditions, such as solvent and pH:
  • the compounds of the general formula (I) contain an acidic proton which can be removed by reaction with a base.
  • bases are, for example, hydrides, hydroxides and carbonates of lithium, sodium, potassium, magnesium and calcium and ammonia and organic amines such as triethylamine and pyridine.
  • Such salts are also the subject of the invention.
  • alkyl radicals having more than two carbon atoms may be straight-chain or branched.
  • Alkyl radicals are, for example, methyl, ethyl, n- or i-propyl, n-, i-, t- or 2-butyl, pentyls, hexyls, such as n-hexyl, i-hexyl and 1,3-dimethylbutyl.
  • Halogen is fluorine, chlorine, bromine or iodine.
  • Tosyl is 4-methylphenylsulfonyl.
  • the multiple bond may be in any position of the radical.
  • the radical propynyl may be 1-propynyl or 2-propynyl.
  • the compounds of the general formula (I) can exist as stereoisomers. For example, if one or more asymmetric carbon atoms are present, enantiomers and diastereomers may occur.
  • Stereoisomers can be obtained from the mixtures obtained in the preparation by customary separation methods, for example by chromatographic separation methods.
  • stereoisomers can be selectively prepared by using stereoselective reactions using optically active sources and / or adjuvants.
  • the invention also relates to all stereoisomers and mixtures thereof which include but are not specifically defined by the general formula (I).
  • the 4- to 7-membered ring formed by the group NR 1 R 2 stands in particular for 1-pyrrolidinyl, 2-isoxazolinyl, 2-isothioazolidinyl, 1-pyrazolidinyl, 3-oxazolidinyl, 3-thiazolidinyl, 1-imidazolidinyl, 1,2 , 4-oxadiazolidin-2-yl, 1,2,4-oxadiazolidin-4-yl, 1,2,4-thiadiazolidin-2-yl, 1,2,4-thiadiazofidin-4-yl, 1,2,4 Triazolidin-1-yl, 1,2,4-triazolidin-2-yl, 1,3,4-oxazolidin-3-yl, 1,3,4-thiadiazolidin-3-yl, 1,3,4-triazolidine 3-yl, 2,3-dihydropyrrol-1-yl, 2,5-dihydropyrrol-1-yl, 2,3-dihydroisoxazol-2-y
  • R 1 and R 2 are independently hydrogen, or by m radicals from the group fluorine, chlorine, bromine, cyano, hydroxy, (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy and (C 1 -C 4 ) alkoxy (C 1 -C 4 ) alkoxy-substituted (C 1 -C 4 ) -alkyl, (C 3 -C 4 ) -alkenyl, (C 3 -C 4 ) -alkynyl, (C 3 -C 6 ) -cycloalkyl, (C 3 -C 6 ) -cycloalkenyl, (C 3 -C 6 ) -cycloalkyl- (C 1 -C 4 ) -alkyl or (C 3 -C 6 ) -cycloalkenyl- (C 1 -C 4 ) -alkyl, wherein R 1
  • R 1 and R 2 independently of one another, denote hydrogen, methyl, butyl, ethyl, propyl, propenyl, propynyl, cyclopropyl, cyclopropylmethyl, methoxyethyl, methoxypropyl, 2-methoxy-1-methylethyl, 2-ethoxy-1-methylethyl, hydroxyethyl or ethoxyethyl, or NR 1 R 2 form a radical from the group 1-pyrrolyl, 1-pyrrolidinyl, 1-pyrazolyl, 1-piperidine, 1-morpholinyl and 1-piperazinyl, by m radicals from the group fluorine, chlorine, bromine, iodine, cyano , Trifluoromethyl, (C 1 -C 4 ) -alkyl and (C 1 -C 4 ) -alkoxy, and the further substituents and indices have the above
  • R 1 and R 2 independently of one another, denote hydrogen, methyl, butyl, ethyl, propyl, propenyl, propynyl, cyclopropyl, cyclopropylmethyl, methoxyethyl, methoxypropyl, 2-methoxy-1-methylethyl, 2-ethoxy-1-methylethyl, hydroxyethyl or ethoxyethyl, or NR 1 R 2 form a radical from the group 1-pyrrolyl, 1-pyrrolidinyl, 1-pyrazolyl, 1-piperidine, 1-morpholinyl and 1-piperazinyl; R 5 is hydrogen, propylsulfonyl, tosyl or 2,6-difluorobenzyl, and the further substituents and indices have the abovementioned meanings.
  • R 5 is hydrogen
  • compounds of the invention in which R 5 is hydrogen may be prepared by base-catalyzed reaction of a benzoyl halide with a pyrazolone, or according to the process shown in scheme 2, and for example, after the process shown in scheme 1 and known from DOS 25 13 750 known methods from EP-A 0 186 117 known methods by base-catalyzed reaction of a Benzoeklarehalogenids with a pyrazolone and subsequent rearrangement in Presence of a base such as triethylamine and a cyanide source such as acetone cyanohydrin, trimethylsilyl cyanide or potassium cyanide are prepared.
  • a base such as triethylamine
  • a cyanide source such as acetone cyanohydrin, trimethylsilyl cyanide or potassium cyanide
  • the compounds of the general formula (1b) can also be prepared directly from the corresponding benzoic acids (IV) in the presence of dehydrating reagents such as DCC or EDAC. These methods are known to the person skilled in the art.
  • the starting compounds used in the above schemes are either commercially available or can be prepared by methods known per se.
  • the pyrazolones of the formula (II) used in the above schemes may be prepared according to WO 97/41106 be prepared known methods.
  • the Benzoeklarehalogenide of the general formula (III) can be prepared by a suitable halogenating agent such as oxalyl chloride or thionyl chloride by known methods from the corresponding benzoic acids (IIIa).
  • the benzoic acids of the general formula (IIIa) can be prepared, for example, from the corresponding 3-fluoro-substituted benzoic acids of the general formula (V) by reacting under suitable conditions with the corresponding amines HNR 1 R 2 (Scheme 4). Suitable conditions are, for example, heating for several hours in an excess of the amine. Such reactions are known to the person skilled in the art.
  • group -NR 1 R 2 can still be derivatized after its introduction, for example by a reductive amination.
  • 4-alkylsulfonyl-3-fluoro-2-methylbenzoic acids of the general formula (VI) can be prepared from 4-chloro-3-fluoro-2-methylbenzoic acids (VII) or their esters by reaction with sodium thioalkylates and subsequent oxidation be obtained with a suitable oxidizing agent.
  • suitable oxidizing agents are, for example, hydrogen peroxide in glacial acetic acid or 3-chloroperbenzoic acid.
  • the compounds of the formula (I) according to the invention have excellent herbicidal activity against a broad spectrum of economically important monocotyledonous and dicotyledonous harmful plants. Even difficult to control perennial weeds, which expel from rhizomes, rhizomes or other permanent organs, are well detected by the active ingredients. It is usually irrelevant whether the substances are applied in the pre-sowing, pre-emergence or postemergence process. Specifically, by way of example, some representatives of the monocotyledonous and dicotyledonous weed flora can be mentioned, which can be controlled by the compounds according to the invention, without the intention of limiting them to certain species.
  • Harmful plants occurring under the specific culture conditions in rice such as Echinochloa, Sagittaria, Alisma, Eleocharis, Scirpus and Cyperus are also excellently controlled by the active compounds according to the invention. If the compounds according to the invention are applied to the surface of the earth before germination, then either the emergence of the weed seedlings is completely prevented or the weeds grow up to the cotyledon stage, but then cease their growth and finally die off completely after a lapse of three to four weeks.
  • the compounds of the invention show excellent activity against Apera spica venti, Chenopodium album, Lamium purpureum, Polygonum convulvulus, Stellaria media, Veronica hederifolia, Veronica persica, Viola tricolor as well as against species of Amaranthus, Galium and Kochia.
  • the compounds of the present invention have excellent herbicidal activity against mono- and dicotyledonous weeds
  • crops of economically important crops such as e.g. Wheat, barley, rye, rice, maize, sugar beet, cotton and soybean are negligibly or not at all damaged.
  • they have excellent compatibility in corn, rice, cereals and soybean.
  • transgenic plants Due to their herbicidal properties, these compounds can also be used for controlling harmful plants in crops of known or yet to be developed genetically modified plants.
  • the transgenic plants are usually characterized by particular advantageous properties, for example by resistance to certain pesticides, especially certain herbicides, resistance to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses.
  • Other special properties relate to z. B. the crop in terms of quantity, quality, shelf life, composition and special ingredients.
  • transgenic plants with increased starch content or altered quality of the starch or those with other fatty acid composition of the crop are known.
  • the compounds of the formula (I) can be used as herbicides in crops resistant to the phytotoxic effects of the herbicides have been made or genetically resistant, in particular soybean and maize.
  • the production of plant cells having a reduced activity of a gene product can e.g. can be achieved by the expression of at least one corresponding antisense RNA, a sense RNA to obtain a cosuppression effect or the expression of at least one appropriately engineered ribozyme which specifically cleaves transcripts of the above gene product.
  • DNA molecules may be used which comprise the entire coding sequence of a gene product, including any flanking sequences that may be present, as well as DNA molecules which comprise only parts of the coding sequence, which parts must be long enough to be present in the cells to cause an antisense effect. It is also possible to use DNA sequences which have a high degree of homology to the coding sequences of a gene product, but are not completely identical.
  • the synthesized protein may be located in any compartment of the plant cell. But to achieve the localization in a particular compartment, z.
  • the coding region can be linked to DNA sequences that ensure localization in a particular compartment.
  • sequences are known to the person skilled in the art (see, for example Braun et al., EMBO J. 11 (1992), 3219-3227 ; Wolter et al., Proc. Natl. Acad. Sci. USA 85 (1988), 846-850 ; Sonnewald et al., Plant J. 1 (1991), 95-106 ).
  • the transgenic plant cells can be regenerated to whole plants by known techniques.
  • the transgenic plants may in principle be plants of any plant species, ie both monocotyledonous and dicotyledonous plants.
  • the active compounds according to the invention in addition to the effects observed in other crops on harmful plants, effects which are specific for the application in the respective transgenic crop often occur, for example a modified or specially extended weed spectrum which can be controlled Application rates that can be used for the application, preferably good combinability with the herbicides to which the transgenic culture is resistant, and influencing growth and yield of the transgenic crops.
  • the invention therefore also relates to the use of the compounds according to the invention as herbicides for controlling harmful plants in transgenic crop plants.
  • the substances according to the invention have excellent growth-regulatory properties in crop plants. They regulate the plant's metabolism and can thus be used to specifically influence plant constituents and facilitate harvesting, such as be used by triggering desiccation and stunted growth. Furthermore, they are also suitable for the general control and inhibition of undesirable vegetative growth, without killing the plants. Inhibition of vegetative growth plays an important role in many monocotyledonous and dicotyledonous cultures, as storage can be reduced or completely prevented.
  • the compounds according to the invention can be used in the form of wettable powders, emulsifiable concentrates, sprayable solutions, dusts or granules in the customary formulations.
  • Another object of the invention therefore also herbicidal agents containing compounds of formula (I).
  • the compounds of the formula (I) can be formulated in various ways, depending on which biological and / or chemical-physical parameters are predetermined.
  • Possible formulation options are, for example: wettable powder (WP), water-soluble powders (SP), water-soluble concentrates, emulsifiable concentrates (EC), emulsions (EW), such as oil-in-water and water-in-oil emulsions, sprayable solutions, suspension concentrates (SC), oil- or water-based dispersions, oil-miscible solutions, dusts (DP), capsule suspensions ( CS), mordants, granules for spreading and soil application, granules (GR) in the form of micro, spray, elevator and adsorption granules, water-dispersible granules (WG), water-soluble granules (SG), ULV formulations, microcapsules and waxes , These individual formulation types are known in principle and are described, for example, in: Winnacker-Kuchler, "Chemical Technology", Volume 7, C.
  • Injectable powders are preparations that are uniformly dispersible in water and contain surfactants of the ionic and / or nonionic type (wetting agents, dispersants), eg polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, 2, in addition to the active ingredient except a diluent or inert substance.
  • surfactants of the ionic and / or nonionic type (wetting agents, dispersants), eg polyoxyethylated alkylphenols, polyoxethylated fatty alcohols, polyoxethylated fatty amines, fatty alcohol polyglycol ether sulfates, alkanesulfonates, alkylbenzenesulfonates, 2, in addition to
  • Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, e.g. Butanol, cyclohexanone, DMF, xylene or higher-boiling aromatics or hydrocarbons or mixtures of these solvents with the addition of one or more surfactants of ionic and / or nonionic type (emulsifiers).
  • organic solvent e.g. Butanol, cyclohexanone, DMF, xylene or higher-boiling aromatics or hydrocarbons or mixtures of these solvents.
  • alkylarylsulfonic acid calcium salts such as calcium dodecylbenzenesulfonate or nonionic emulsifiers
  • fatty acid polyglycol esters alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide-ethylene oxide condensation products, alkyl polyethers, sorbitan esters e.g. Sorbitan fatty acid esters or polyoxethylenesorbitan esters such as e.g. Polyoxyethylene sorbitan fatty acid esters.
  • Dusts are obtained by milling the active ingredient with finely divided solids, e.g. Talc, natural clays such as kaolin, bentonite and pyrophyllite, or diatomaceous earth.
  • Suspension concentrates may be water or oil based. They can be prepared, for example, by wet grinding using commercially available bead mills and, if appropriate, addition of surfactants, as described, for example, in US Pat. are already listed above for the other formulation types.
  • Emulsions e.g. Oil-in-water (EW) emulsions may be prepared, for example, by means of stirrers, colloid mills and / or static mixers using aqueous organic solvents and optionally surfactants such as those described e.g. listed above for the other formulation types.
  • EW Oil-in-water
  • Granules can either be prepared by spraying the active ingredient onto adsorptive, granulated inert material or by applying active substance concentrates by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or mineral oils, to the surface of carriers such as sand, kaolinites or granulated inert material.
  • adhesives for example polyvinyl alcohol, sodium polyacrylate or mineral oils
  • suitable active ingredients in the usual manner for the production of fertilizer granules - if desired in Mixture with fertilizers - be granulated.
  • Water-dispersible granules are generally prepared by the usual methods such as spray drying, fluidized bed granulation, plate granulation, mixing with high-speed mixers and extrusion without solid inert material.
  • the agrochemical preparations generally contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of active compound of the formula (I).
  • the drug concentration is e.g. about 10 to 90 wt .-%, the balance to 100 wt .-% consists of conventional formulation ingredients.
  • the active ingredient concentration may be about 1 to 90, preferably 5 to 80 wt .-%.
  • Dusty formulations contain 1 to 30 wt .-% of active ingredient, preferably usually 5 to 20 wt .-% of active ingredient, sprayable solutions contain about 0.05 to 80, preferably 2 to 50 wt .-% of active ingredient.
  • the active ingredient content depends, in part, on whether the active compound is liquid or solid and which granulating aids, fillers, etc. are used.
  • the content of active ingredient is, for example, between 1 and 95% by weight, preferably between 10 and 80% by weight.
  • the active substance formulations mentioned optionally contain the customary adhesion, wetting, dispersing, emulsifying, penetrating, preserving, antifreeze and solvent, fillers, carriers and dyes, antifoams, evaporation inhibitors and the pH and the Viscosity-influencing agent.
  • the formulations present in commercially available form are optionally diluted in customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and water-dispersible granules by means of water. Dusty preparations, ground or spreading granules and sprayable Solutions are usually no longer diluted with other inert substances before use.
  • the external conditions such as temperature, humidity, the type of herbicide used, inter alia, the required application rate of the compounds of the formula (I) varies. It can vary within wide limits, for example between 0.001 and 1.0 kg / ha or more of active substance, but is preferably between 0.005 and 750 g / ha, especially between 0.005 and 250 g / ha.
  • Step 4 3 - [(3-Methoxypropyl) amine] -2-methyl-4- (methylsulfonyl) benzoic acid
  • Step 5 (3-Cyclopropyl-5-hydroxy-1-methyl-1H-pyrazol-4-yl) [3 - [(3-methoxy-propyl) -amino] -2-methyl-4- (methylsulfonyl) -phenyl] -methanone
  • Step 1 3 - [(2-Methoxyethyl) (methyl) amino] -2-methyl-4- (methylsulfonyl) benzoic acid
  • Step 2 (3-Cyclopropyl-5-hydroxy-1-methyl-1H-pyrazol-4-yl) [3 - [(2-methoxyethyl) (methyl) amino] -2-methyl-4- (methylsulfonyl) phenyl ] methanone
  • a dust is obtained by mixing 10 parts by weight of a compound of general formula (I) and 90 parts by weight of talc as an inert material and comminuting in a hammer mill.
  • a wettable powder readily dispersible in water is obtained by mixing 25 parts by weight of a compound of the general formula (I), 64 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurate as a wetting and dispersing agent, and grinded in a pin mill.
  • a dispersion concentrate readily dispersible in water is obtained by reacting 20 parts by weight of a compound of the general formula (I), 6 parts by weight of alkylphenol polyglycol ether (®Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 EO) and 71% by weight.
  • Parts of paraffinic mineral oil (boiling range, for example, about 255 to about 277 ° C) mixed and ground in a ball mill to a fineness of less than 5 microns.
  • An emulsifiable concentrate is obtained from 15 parts by weight of a compound of general formula (I), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol as emulsifier.
  • a water-dispersible granule is obtained by 75 parts by weight of a Compound of the general formula (I) 10 " lignosulfonic acid calcium, 5 " sodium lauryl sulfate, 3 " Polyvinyl alcohol and 7 " kaolin milled, ground on a pin mill and granulated the powder in a fluidized bed by spraying water as Granulier crampkeit.
  • a water-dispersible granule is also obtained by 25 parts by weight of a Compound of the general formula (I) 5 " 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium, 2 " oleoylmethyl tauric acid sodium, 1 " polyvinyl alcohol, 17 " Calcium carbonate and 50 " water Homogenized on a colloid mill and pre-crushed, then ground on a bead mill and the suspension thus obtained in a spray tower by means of a Einstoffdüse atomized and dried.
  • Seeds of monocotyledonous and dicotyledonous harmful plants as well as seeds of maize, soybean and wheat are laid out in sandy soil in cardboard pots and covered with soil.
  • the compounds according to the invention formulated in the form of wettable powders or emulsion concentrates and known from the prior art are then applied as an aqueous suspension or emulsion having a water application rate of 600 to 800 l / ha in a dosage indicated in Tables 1 to 10 Surface of the cover soil applied.
  • the pots are placed in the greenhouse and kept under good growth conditions for the harmful and crop plants.
  • the optical assessment of plant damage and / or run-on damage occurs after emergence of the plants after a test period of 3 to 4 weeks. It is found that the compounds of the invention have the same or better herbicidal action less damage to crop plants, as the compounds known from the prior art (Comparison Tables 1 to 4, 6 to 10).
  • Seeds of monocotyledonous and dicotyledonous harmful plants, as well as seeds of maize, soybean and wheat are laid out in sandy loam soil in cardboard pots, covered with soil and grown in the greenhouse under good growth conditions. Two to three weeks after sowing, the pollinated and cultivated plants are treated in a trefoil study.
  • the compounds according to the invention which are formulated as wettable powders or as emulsion concentrates and those known from the prior art are sprayed onto the surface of the green parts of the plant at a dosage of water of 600 to 800 l / ha in a dosage indicated in Tables 1 to 10. After 3 to 4 weeks of life of the test plants in the greenhouse under optimal growth conditions, the effect of the compounds in comparison with compounds disclosed in the prior art, scored. It is found that the compounds of the invention with the same or better herbicidal effect cause less damage to crop plants, as known from the prior art compounds (Comparison Tables 1 to 4, 6 to 10).
  • Herbicidal action Damage to crops DIGSA ECHCG MATIN VIOTR ZEAMX No. 3 80 90% 90% 70% 90% 30% S2 80 80% 80% 30% 80% 60% connection Dosage [g ai / ha] Herbicidal action Damage to crops GALAP VERPE GLXMA ORYSA No.4 20 80% 60% 0% 0% S3 20 40% 20% 20% 30% connection Dosage [g ai / ha] Herbicidal action Damage to crops GALAP MATIN STEMS GLXMA ZEAMX No. 5 80 80% 50% 100% 0% 10% S4 80 80% 30% 100% 50% 30% connection Dosage [g ai / ha] Herbicidal action Damage to crops MATIN STEMS ZEAMX No.

Claims (11)

  1. Composés de formule (I) ou leurs sels
    Figure imgb0052
     où
    R1 et R2, indépendamment l'un de l'autre, représentent un atome d'hydrogène, un groupe furan-2-yle, tétrahydrofuran-2-yl-méthyle,
    ou un groupe alkyle en C1-C4, alcényle en C3-C4, alcynyle en C3-C4, cycloalkyle en C3-C6, cycloalcényle en C3-C6, (cycloalkyl en C3-C6)-(alkyle en C1-C4) ou (cycloalcényl en C3-C6)-(alkyle en C1-C4) substitué par m radicaux pris dans le groupe constitué par un atome de fluor, de chlore, de brome, un groupe cyano, hydroxy, alkyle en C1-C4, alkoxy en C1-C4 et (alkoxy en C1-C4)-(alkoxy en C1-C4),
    où R1 et R2 ne représentent pas simultanément un atome d'hydrogène,
    ou
    NR1R2 représente un cycle de 4 à 7 chaînons saturé, partiellement saturé, complètement insaturé ou aromatique contenant en tant que chaînons n hétéroatomes pris dans le groupe constitué par un atome d'azote, d'oxygène et de soufre, qui est substitué par m radicaux pris dans le groupe constitué par un atome de fluor, de chlore, de brome, d'iode, un groupe cyano, hydroxy, trifluorométhyle, nitro, alkyle en C1-C4, alkoxy en C1-C4, fluoroalkyle en C1-C3, fluoroalkoxy en C1-C3 ou alkoxyméthyle en C1-C3 ;
    R3 représente un groupe méthyle, éthyle ou iso-propyle ;
    R4 représente un groupe alkyle en C1-C4, alcényle en C3-C4 ou alcynyle en C3-C4 ;
    R5 représente un atome d'hydrogène, un groupe (alkyl en C1-C4) sulfonyle, (alcényl en C3-C4) sulfonyle, (alcynyl en C3-C4) sulfonyle,
    ou un groupe phénylsulfonyle ou benzyle substitué par m radicaux pris dans le groupe constitué par un atome de fluor, de chlore, de brome, un groupe cyano, trifluorométhyle, nitro, méthyle, éthyle, méthoxy et éthoxy ;
    m vaut 0, 1, 2 ou 3 ;
    n vaut 1, 2 ou 3.
  2. Composés selon la revendication 1, où
    R1 et R2, indépendamment l'un de l'autre, représentent un atome d'hydrogène,
    ou un groupe alkyle en C1-C4, alcényle en C3-C4, alcynyle en C3-C4, cycloalkyle en C3-C6, cycloalcényle en C3-C6, (cycloalkyl en C3-C6) - (alkyle en C1-C4) ou (cycloalcényl en C3-C6) - (alkyle en C1-C4) substitué par m radicaux pris dans le groupe constitué par un atome de fluor, de chlore, de brome, un groupe cyano, hydroxy, alkyle en Ci-C4, alkoxy en C1-C4 et (alkoxy en C1-C4) - (alkoxy en C1-C4), où R1 et R2 ne représentent pas simultanément un atome d'hydrogène,
    ou
    NR1R2 représente un cycle de 4 à 7 chaînons saturé, partiellement saturé, complètement insaturé ou aromatique contenant en tant que chaînons n hétéroatomes pris dans le groupe constitué par un atome d'azote, d'oxygène et de soufre, qui est substitué par m radicaux pris dans le groupe constitué par un atome de fluor, de chlore, de brome, d'iode, un groupe cyano, trifluorométhyle, nitro, alkyle en C1-C4, alkoxy en C1-C4, fluoroalkyle en C1-C3, fluoroalkoxy en C1-C3 ou alkoxyméthyle en C1-C3.
  3. Composés selon la revendication 1 ou 2,
    où
    R1 et R2, indépendamment l'un de l'autre, représentent un atome d'hydrogène, un groupe méthyle, butyle, éthyle, propyle, propényle, propynyle, cyclopropyle, cyclopropylméthyle, méthoxyéthyle, méthoxypropyle, 2-méthoxy-1-méthyléthyle, 2-éthoxy-1-méthyléthyle, hydroxyéthyle ou éthoxyéthyle,
    ou
    NR1R2 forment un radical pris dans le groupe constitué par 1-pyrrolyle, 1-pyrrolidinyle, 1-pyrazolyle, 1-pipéridine, 1-morpholinyle et 1-pipérazinyle, qui est substitué par m radicaux pris dans le groupe constitué par un atome de fluor, de chlore, de brome, d'iode, un groupe cyano, trifluorométhyle, alkyle en C1-C4 et alkoxy en C1-C4.
  4. Composés selon l'une des revendications 1 à 3, où
    R1 et R2, indépendamment l'un de l'autre, représentent un atome d'hydrogène, un groupe méthyle, butyle, éthyle, propyle, propényle, propynyle, cyclopropyle, cyclopropylméthyle, méthoxyéthyle, méthoxypropyle, 2-méthoxy-1-méthyléthyle, 2-éthoxy-1-méthyléthyle, hydroxyéthyle ou éthoxyéthyle,
    ou
    NR1R2 forment un reste pris dans le groupe constitué par 1-pyrrolyle, 1-pyrrolidinyle, 1-pyrazolyle, 1-pipéridine, 1-morpholinyle et 1-pipérazinyle et
    R5 représente un atome d'hydrogène, un groupe propylsulfonyle, tosyle ou 2,6-difluorobenzyle.
  5. Composés selon l'une des revendications 1 à 4, où
    R3 représente un groupe méthyle ou éthyle ;
    R4 représente un groupe méthyle ou éthyle, et
    R5 représente un atome d'hydrogène.
  6. Agent herbicide, caractérisé par une teneur à efficacité herbicide en au moins un composé de formule générale (I) selon l'une des revendications 1 à 5.
  7. Agent herbicide selon la revendication 6 en mélange avec des formulants.
  8. Procédé pour la lutte contre les plantes indésirables, caractérisé en ce qu'une quantité efficace d'au moins un composé de formule générale (I) selon l'une des revendications 1 à 5 ou d'un agent herbicide selon la revendication 6 ou 7 est appliquée aux plantes ou au site de croissance des plantes indésirables.
  9. Utilisation de composés de formule générale (I) selon l'une des revendications 1 à 5 ou d'agents herbicides selon la revendication 6 ou 7, pour la lutte contre les plantes indésirables.
  10. Utilisation selon la revendication 9, où les composés de formule générale (I) sont utilisés pour la lutte contre les plantes indésirables dans les cultures de plantes utiles.
  11. Utilisation selon la revendication 9 ou 10, où les plantes utiles sont les plantes utiles transgéniques.
EP05807937A 2004-12-09 2005-11-10 3-cyclopropyl-4-(3-amino-2-methylbenzoyl)pyrazoles et leur utilisation comme herbicides Not-in-force EP1824338B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL05807937T PL1824338T3 (pl) 2004-12-09 2005-11-10 3-Cyklopropylo-4-(3-amino-2-metylobenzoilo)pirazole i ich zastosowanie jako herbicydów

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004059302A DE102004059302A1 (de) 2004-12-09 2004-12-09 3-Cyclopropyl-4-(3-amino-2-methylbenzoyl)pyrazole und ihre Verwendung als Herbizide
PCT/EP2005/012010 WO2006061074A1 (fr) 2004-12-09 2005-11-10 3-cyclopropyl-4-(3-amino-2-methylbenzoyl)pyrazoles et leur utilisation comme herbicides

Publications (2)

Publication Number Publication Date
EP1824338A1 EP1824338A1 (fr) 2007-08-29
EP1824338B1 true EP1824338B1 (fr) 2008-03-19

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EP05807937A Not-in-force EP1824338B1 (fr) 2004-12-09 2005-11-10 3-cyclopropyl-4-(3-amino-2-methylbenzoyl)pyrazoles et leur utilisation comme herbicides

Country Status (16)

Country Link
US (1) US7396939B2 (fr)
EP (1) EP1824338B1 (fr)
JP (1) JP2008522990A (fr)
KR (1) KR20070089944A (fr)
CN (1) CN101072503B (fr)
AT (1) ATE389326T1 (fr)
AU (1) AU2005313613A1 (fr)
BR (1) BRPI0518519B1 (fr)
CA (1) CA2590078A1 (fr)
DE (2) DE102004059302A1 (fr)
EA (1) EA200701236A1 (fr)
ES (1) ES2301075T3 (fr)
IL (1) IL183465A0 (fr)
MX (1) MX2007006970A (fr)
PL (1) PL1824338T3 (fr)
WO (1) WO2006061074A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005028294A1 (de) * 2005-06-18 2006-12-21 Bayer Cropscience Gmbh Verfahren zum Herstellen von Carboxamiden
EP1980553A1 (fr) * 2007-04-12 2008-10-15 Bayer CropScience Aktiengesellschaft 4-(3-Aminobenzoyl)-1-méthylpyrazole et son utilisation en tant qu'herbicide
DE102007026875A1 (de) * 2007-06-11 2008-12-24 Bayer Cropscience Ag 3-Cyclopropyl-4-(3-thiobenzoyl)pyrazole und ihre Verwendung als Herbizide
CN103980202B (zh) * 2014-05-27 2017-01-18 青岛清原化合物有限公司 一种具有除草活性的4‑苯甲酰吡唑类化合物

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR006793A1 (es) * 1996-04-26 1999-09-29 Ishihara Sangyo Kaisha Compuestos pirazol o sus sales y herbicidas conteniendo los mismos
AR012142A1 (es) * 1997-03-24 2000-09-27 Dow Agrosciences Llc Compuestos de 1-alquil-4-benzoil-5-hiroxipirazol, composiciones herbicidas que los contienen; metodo para controlar vegetacion no deseada y compuestosintermediarios utiles para preparar dichos compuestos
JPH11292849A (ja) * 1998-04-03 1999-10-26 Nippon Soda Co Ltd ベンゾイルピラゾール化合物および除草剤
DE10157545A1 (de) * 2001-11-23 2003-06-12 Bayer Cropscience Gmbh Herbizide Mittel enthaltend Benzoylpyrazole und Safener
DE102004016496A1 (de) * 2004-04-03 2005-10-20 Bayer Cropscience Gmbh Herbizid wirksame 3-Amino-2-thiomethyl-benzoylpyrazole

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Publication number Publication date
DE102004059302A1 (de) 2006-06-14
US20060128568A1 (en) 2006-06-15
KR20070089944A (ko) 2007-09-04
EP1824338A1 (fr) 2007-08-29
BRPI0518519B1 (pt) 2014-11-25
EA200701236A1 (ru) 2007-10-26
JP2008522990A (ja) 2008-07-03
WO2006061074A1 (fr) 2006-06-15
BRPI0518519A2 (pt) 2008-11-25
CN101072503A (zh) 2007-11-14
PL1824338T3 (pl) 2008-08-29
US7396939B2 (en) 2008-07-08
ATE389326T1 (de) 2008-04-15
DE502005003395D1 (de) 2008-04-30
CN101072503B (zh) 2013-03-27
ES2301075T3 (es) 2008-06-16
AU2005313613A1 (en) 2006-06-15
IL183465A0 (en) 2007-09-20
CA2590078A1 (fr) 2006-06-15
MX2007006970A (es) 2007-09-11

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